New nematocidal compositions

ABSTRACT

This invention discloses nematocidal compositions comprising an inert carrier and, as an essential active ingredient, in a quantity toxic to nematodes, a compound of the formula   WHEREIN R1 and R2 are alkyl; X1, X2, X3 and X4 are independently selected from the group consisting of oxygen and sulfur; m and n are each integers from 0 to 1; Z1 is selected from the froup consisting of alkyl, alkenyl and WHEREIN B is selected from the group consisting of alkyl, alkenyl, alkoxy, alkylthio, halogen, nitro, alkylsulfoxide, alkylsulfone and dialkylamino, r is an integer from 0 to 5, Q is selected from the group consisting of oxygen, sulfur, alkylene, alkyleneoxy and alkylenethio, and t is an integer from 0 to 1. This invention further discloses a method for control of nematodes which comprises contacting said nematodes with a nematocidal composition comprising a inert carrier and, in a quantity toxic to nematodes, a compound as described above.   WHEREIN A is selected from the group consisting of alkyl, alkenyl, alkoxy, alkylthio, halogen, nitro, alkylsulfoxide, alkylsulfone and dialkylamino, q is an integer from 0 to 5, and p is an integer from 0 to 3; Z2 is selected from the group consisting of hydrogen and Z1, provided that when Z2 is hydrogen then n is 0; and Y is selected from the group consisting of alkyl, alkenyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino and

United States Patent Sidney B. Richter Chicago;

Ephraim H. Kaplan, Skokie, both of Ill. [21] Appl. No. 799,1 15

[72] Inventors [22] Filed Feb. 13, 1969 [45] Patented Nov. 23, 1971 [73]Assignee Velsicol Chemical Corporation Chicago, Ill.

[54] NEW NEMATOCIDAL COMPOSITIONS 8 Claims, No Drawings PrimaryExaminer-Albert T. Meyers Assistant Examiner-Norman A. Drezin Attomey-Robert J. Schwarz ABSTRACT: This invention discloses nematocidalcompositions comprising an inert carrier and, as an essential activeingredient, in a quantity toxic to nematodes, a compound of the formulawherein R and R are alkyl; X, X X and X are independently selected fromthe group consisting of oxygen and sulfur; m and n are each integersfrom 0 to 1; Z' is selected from the group consisting of alkyl allgenyland wherein A is selected from the group consisting of alkyl, alkenyl,alkoxy, alkylthio, halogen, nitro, alkylsulfoxide, alkylsulfone anddialkylamino, q is an integer from 0 to 5, and p is an integer from 0 to3; Z is selected from the group consisting of hydrogen and 2', providedthat when 2 is hydrogen then n is 0; and Y is selected from the groupconsisting of alkyl, alkenyl, alkoxy, alkylthio, amino, alkylamino,dialkylamino and wherein B is selected from the group consisting ofalkyl. alkenyl, alkoxy, alkylthio, halogen, nitro, alkylsulfoxide,alkylsulfone and dialkylamino, r is an integer from 0 to 5, Q isselected from the group consisting of oxygen, sulfur, alkylene,alkyleneoxy and alkylenethio, and I is an integer from 0 to 1. Thisinvention further discloses a method for control of nematodes whichcomprises contacting said nematodes with a nematocidal compositioncomprising a inert carrier and, in a quantity toxic to nematodes, acompound as described above.

NEW NEMATOCIDAL COMPOSITIONS This invention relates to new pesticidalcompositions and more particularly relates to nematocidal compositionscomprising an inert carrier and, as an essential active ingredient, in aquantity toxic to nematodes, a compound of the formula ts-r) wherein Bis selected from the group consisting of alkyl, alkenyl, alkoxy,alkylthio, halogen, nitro, alkylsulfoxide, alkylsulfone anddialkylamino, r is an integer from to 5, Q is selected from the groupconsisting of oxygen, sulfur, alkylene, alkyleneoxy and alkylenethio,and t is an integer from 0 to 1.

This invention further relates to a method of controlling nematodeswhich comprises contacting said nematodes with a nematocidal compositionas described above.

In a preferred embodiment of the present invention the nematocidallyactive compounds of formula I have substituents as follows: R and R arelower alkyl; X, X, X and X are independently selected from the groupconsisting of oxygen and sulfur; m and n are each integers from 0 to 1;Z is selected from the group consisting of lower alkyl, lower alkenyland wherein A is selected from the group consisting of lower alkyl,lower alkenyl, lower alkoxy, lower alkylthio, chlorine, bromine, nitroand di(lower alkyl)amino, q is an integer from 0 to 3, and p is aninteger from 0 to 3; Z is selected from the group consisting of hydrogenand the preferred 2, provided that when Z is hydrogen then n is 0; and Yis selected from the group consisting of lower alkyl, lower alkenyl,lower alkoxy, lower alkylthio, amino, lower alkylamino, di(loweralkyl)amino and wherein B is selected from the group consisting of loweralkyl, lower alkenyl, lower alkoxy, lower alkylthio, chlorine,

bromine, nitro and di( lower alkyl )amino, r is an integer fromil to 3,Q is selected from the group consisting of oxygen, sulfur, loweralkylene, lower alkyleneoxy and lower alkylenethio, and r is an integerfrom 0 to l.

The nematocidally active compounds of the present invention can bereadily prepared from compounds of the formula (Hal)CH-C=NOR wherein Haldesignates halogen, preferably chlorine or bromine, and R, R, X, Z and nare as heretofore described, by reaction with about an equimolar amountof an alkali metal phosphonamidate, phosphoramidate, phosphate,phosphonate, or phosphinate of the formula XI Z -(X )mI X M 3'! (III)wherein M is an alkali metal and X, X X", Z, Y and m are as heretoforedescribed. This reaction can be effected by heating the reactants in aninert organic solvent such as methyl ethyl ketone at the refluxtemperature of the reaction mixture for a period of from about 4 toabout 24 hours. After the reaction is completed the reaction mixture canbe filtered to remove the alkali metal halide which has formed. Thedesired product can then be conveniently recovered as a residue uponevaporation of the solvent from the remaining solution. The product canthen be used as such or can be further purified by washing, distillationor chromatography if the product is an oil, or by trituration,recrystallization or other common methods well known in the art if theproduct is a solid.

The compounds of formula ll can be prepared from a compound of theformula Z (IV) wherein Hal stands for halogen, such as chlorine orbromine, and R, X, Z and n are as heretofore described, by reaction witha diazoalkane. This reaction can be effected by slowly adding a solutionof the alkoxyacetamide of formula IV with stirring to a slight molarexcess of a solution of the diazoalkane at a temperature below about 15C. and preferably at a temperature of from about l0 to about 10 C.Suitable solvents for the reactants are inert organic solvents such asether, benzene or ether-ethanol mixtures, and the like. After theaddition is completed stirring can be continued for a short period toinsure completion of the reaction. The desired product can then berecovered by evaporation of the solvents used and can then be used assuch or can be further purified by conventional techniques well known inthe art.

Exemplary diazoalkanes suitable for reaction with compounds of formula[V to form the compound of formula ll are diazomethane, diazoethane,diazo-n-propane, diazo-isobutane, diazo-n-butane, diazo-n-pentane,diazo-n-hexane, diazon-octane, and the like.

Exemplary suitable compounds of formula IV for preparing the compoundsof formula ll are N-methoxy-a-chloroacetamide,N-ethoxy-a-chloroacetamide, N-isopropoxy-achloroacetamide,N-n-propoxy-a-bromoacetamide, N-butoxy-a-chloroacetamide,n-nonoxy-a-chloroacetamide, N- methoxy-a-chloropropionamide,N-methoxy-a-chloro-n-butyramide, N-ethoxy-a-chloroisobutyramide.N-methoxy-achloro-n-valeramide, N-isopropoxy-a-chloro-n-caproamide,N-methoxy-a-phenyl-a-chloroacetamide, N-methoxy-a-(4- chlorophenyl)-a-chloroacetamide, N-methoxy-a-( 2-methyl-4-chlorophenyl)-achloroacetamide, N-ethoxy-a-( 3- nitrophenyl)-a-chloroacetamide, N-methoxy-a-( 3-dimethylaminophenyl)-a-chloroacetamide, N-ethoxy-a-(2,4-dichlorobenzyl)-a-chloroacetamide, and the like.

The alkali metal phosphonamidates, phosphoramidates, phosphates,phosphonates and phosphinates of formula III which are used in thepreparation of the active compounds of the present invention are knownin the art and can be prepared by the methods described by Malatesta andPizzotti, Chimica e lndustria (Milan) 27, 6-10( 1945,), and Melnikov andGrapov, Zhur. Vsesoyuz Khim. Obschchestva in D.1. Mendeleeva, 6, No. 1;119-120( 1961).

The manner in which the nematocidally active compounds of the presentinvention can be prepared is more specifically illustrated in thefollowing examples.

EXAMPLE 1 Preparation of l-Chloro-2-methoxyimino-2-methoxyethane Ether(275ml.) was added to a 40 allylphenyl) percent 'aqueous solution ofpotassium hydroxide (85 ml.) contained in a 500 ml. Erlenmeyer flask andthe resulting mixture was cooled in an ice-salt bath to C. with stirringin the absence *of light. N-Nitrosomethylurea (30 grams; 0.29 mol) wasadded over a period of about 3 minutes with stirring and continuedcooling. The ether phase was then decanted into a cooled 1- liter flaskand a solution of N-methoxy-chloroacetamide (20 grams; 0.16 mol) inether and ethyl alcohol was slowly added, with stirring and cooling,over a period of about 2 hours. Stirring and cooling was continued forabout 4 hours after the addition was completed. The reaction mixture wasthen allowed to warm up to room temperature and dried over anhydrousmagnesium sulfate. After this time the mixture was filtered and thefiltrate was stripped of solvents. The residue was distilled and thefraction boiling between 61 and 70 C. at 20 mm. of Hg pressure wascollected to yield l-chloro-Z-methoxyimino-Z-methoxyethane.

EXAMPLE 2 Preparation of S-( 2-Methoxyimino-Zmethoxyethyl) O-EthylN-lsopropylthiolophosphoramidate A solution ofl-chloro-2methoxyimino-Z-methoxyethane (7 grams; 0.05 mol) in methylethyl ketone 100 ml.) was placed in a glass reaction flask equipped withmechanical stirrer and reflux condenser. Potassium O-ethyl N-isopropylthiolophosphoramidate (l 1 grams; 0.05 mol) was added theretoand the reaction mixture was heated at reflux for a period of about 21hours with continuous stirring. After this time the reaction mixture wascooled and filtered to remove the potassium chloride which had formed.The filtered solution was then stripped of solvent in a rotaryevaporator and the resulting product was chromatographed in a37-inchlong column of l-inch diameter utilizing florex (300 grams) asthe adsorbent and various mixtures of pentane, ether and 'acetone as theeluants. Thirty-one fractions were collected of ate 31 had a refractiveindex of 1.4902 at 25' Gland the following elemental analysis ascalculated for C,H,,N,O PS:

Theoretical '1' 9.9 10.9 1 1.3 Found a 9.08 10.54 11.13

EXAMPLE 3 Preparation of l-Chloro-Z-methoxyiminoQ-ethoxyethane Ether(275 ml.) was added to a 40 percent aqueous solution of potassiumhydroxide ml.) and the resulting mixture was stirred and cooled to about5' C. in the absence of light. N- Nitrosoethylurea (35.5 grams; 0.29mol) was slowly added over a period of about 10 minutes with stirringand continued cooling. The ether phase was then decanted into aprecooled l-liter flask and a solution of N-methoxy-a-chloroacetarnide(20 grams; 0.16 mol) in an ethanol-ether mixture (200 ml.) was slowlyadded over a period of about minutes. Stirring and cooling was continuedfor a period of about 1 hour after the addition was completed. Afterthis time the reaction mixture was allowed to warm up to roomtemperature and was dried over anhydrous magnesium sulfate. The driedsolution was filtered and then stripped of solvents. The residue wasdistilled in vacuo to yield l-chloro-2-methoxyimino-2-cthoxyethanehaving a boiling point of 53' C. at l 8 mm. Hg pressure and having thefollowing elemental analysis as calculated for C,H, ClNO,:

Theoretical i:

Found k 6.62

/III

l-Chloro-2-methoxyimino-2-ethoxyethane(4.5 grams; 0.03 mol), potassiumO-ethyl N-isopropylthiolophosphoramidate (6.5 grams; 0.03 mol) andmethyl ethyl ketone ml.) were charged into a glass reaction flaskequipped with stirrer and reflux condenser. The reaction mixture washeated at reflux for a period of about 16 hours with continuousstirring. After this time the reaction mixture was cooled and filteredto remove the potassium chloride which had formed. The filtered solutionwas then evaporated under reduced pressure and the residue dissolved inan ether-methylene chloride mixture. The resulting solution was washedwith water and was dried over anhydrous magnesium sulfate and filtered.The filtered solution was then stripped of solvents under reducedpressure to yield S-(2-methoxyirnino-2-ethoxyethyl) O-ethyl N-isopropylthiolophosphoramidate having a refractive index of 1.4790 at 23C. and having the following elemental analysis as calculated for C H N OPS:

C H1 S Theoretical 40.3 7.8 10.4 10.7

Found 1: 39.99 7.69 10.72 10.77

EXAMPLE 5 Preparation ofO-(Z-Methoxyimino-Z- methoxyethyl) O-MethylN,N-Dimethylphosphoramidate A solution ofl-chloro-2-methoxyimino-Z-methoxy-ethane (7 grams; 0.05 mol) in methylethyl ketone 100 ml.) is placed into a glass reaction flask equippedwith a mechanical stirrer and reflux condenser. Potassium O-methyl N,N-dimethylphosphoramidate (8.9 grams; 0.05 mol) is added and the reactionmixture is heated at reflux with stirring, for a period of about 18hours. After this time the reaction mixture is cooled and filtered toremove the potassium chloride which is fonned. The filtered solution isthen stripped of solvent under reduced pressure and the residue isredissolved in an ether-methylene chloride mixture. The resultingsolution is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is then filtered and evaporated to yieldO-(2-methoxyimino-Z-methoxyethyl) O-methyl N,N- dimethylphosphoramidate.

EXAMPLE 6 Preparation of l-Chloro-Z-n-butoxyimino-2-ethoxyethane Afreshly prepared solution of diazoethane (6 grams; 0.1 mol) in either(100 ml.) is charged into a liter glass reaction flask equipped with amagnetic stirrer and is cooled to a temperature of about 5 C. A solutionof N-n-butoxy-achloroacetarnide (17 grams; 0.] mol) in a 1:1 mixture ofethanol and ether (200 ml.) is then slowly added to the flask, withcontinuous stirring and cooling, over a period of about 1 hour. Afterthe addition is completed stirring is continued for about 2 hours. Afterthis time the mixture is filtered and the filtrate is stripped ofsolvents under reduced pressure to yieldl-chloro-2-n-butoxyimino-Z-ethoxyethane as a residue.

EXAMPLE 7 Preparation of O-( 2-n-Butoxyimino-2- ethoxyethyl)O-(4-Chlorophenyl) N,N-diethylphosphoramidate O O-CgHs C 115 C H Asolution of l-chloro-2-n-butoxyimino-2-ethoxyethane (9.7 grams; 0.05mol) in methyl ethyl ketone (100 ml.) is placed into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. PotassiumO-(4-chlorophenyl) N,N-diethylphosphoramidate grams; 0.05 mol) is addedand the reaction mixture is heated at reflux, with stirring, for aperiod of about 18 hours. After this time the reaction mixture is cooledand filtered to remove the potassium chloride which has formed. Thefiltered solution is then is then stripped of solvent under reducedpressure and the residue is redissolved in an ether-methylene chloridemixture. The resulting solution is washed with water and is dried overanhydrous magnesium sulfate. The dried solution is then filtered andevaporated to yield O-(2-n-butoxylimino-2-ethoxyethyl)O-(4-chlorophenyl) N,N-diethylphosphoramidate.

EXAMPLE 8 Preparation of l-Chloro-Z-isopropoxyimino-Z-methoxyethane Afreshly prepared solution of diazomethane (4.2 grams; 0.1 mol) in ether(100 ml.) is placed into a l-liter glass reaction vessel equipped with amagnetic stirrer and is cooled to a temperature of about 0 C. A solutionof N-isopropoxy-achloroacetamide (15.2 grams; 0.1 mol) in a lzl mixtureof ethanol and ether 200 ml.) is then added to the reaction vessel, withcontinuous stirring and cooling, over a period of about 2 hours.Stirring is continued for a further period of about 3 hours after theaddition is completed. After this time the mixture is filtered and thefiltrate is stripped of solvents under reduced pressure to yieldlchloro-2-isopropoxyimino- 2-methoxyethane as a residue.

EXAMPLE 9 Preparation of O-(2-lsopropoxyimino- 2-methoxyethyl) S-(3-Methylphenyl) N-n-propylthiolophosphoramidate yethane (8.5 grams; 0.05mol) in methyl ethyl ketone (100 ml.) is placed into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. PotassiumS-(3- methylphenyl) Nn-propylthiolophosphoramidate l 1.9 grams; 0.05mol) is added to the flask and the reaction mixture is heated at refluxfor a period of about 12 hours. After this time the mixture is cooledand filtered to remove the potassium chloride which has formed. Thefiltered solution is then stripped of solvent under reduced pressure andthe residue is redissolved in an ether-methylene chloride mixture. Theresulting solution is washed with water and dried over anhydrousmagnesium sulfate. The dried solution is filtered and stripped ofsolvent under reduced pressure to yield O-(2-isopropoxyimino-2-methoxyethyl) S-(3-methylphenyl)N-npropylthiolophosphoramidate as a residue.

EXAMPLE 10 Preparation of l-Methoxyiminol methoxy 2-chloropropane Ether(275 ml.) is added to a 40 percent aqueous solution of potassiumhydroxide ml.) contained in a 500 ml. Erlenmeyer flask and the resultingmixture is cooled in an ice-salt bath to 5 C., with stirring, in theabsence of light. N- Nitrosomethylurea (30 grams; 0.29 mol) is addedover a period of about 3 minutes with stirring and continued cooling.The ether phase is then decanted into a cooled l-liter flask and asolution of N-methoxy-a-chloropropionamide (21 grams; 0.l6 mol) in etherand ethyl alcohol is slowly added, with stirring and cooling, over aperiod of about 2 hours. Stirring and cooling is continued for about 4hours after the addition is completed. The reaction mixture is thenallowed to warm up to room temperature, dried over magnesium sulfate andfiltered. The filtrate is stripped of solvents to yield 1- methoxyiminol-methoxy-2-chloropropane.

EXAMPLE 11 Preparation of S-( l-Methyl-2-methoxyimino-2-methoxyethyl)O-Ethyl N-lsopropylthiolophosphoramidate OCH C CH;

A solution or l meth oxyimino-l-methoxy-2-chloropropane (7.6 grams; 0.05mol) in methyl ethyl ketone (100 ml.) is charged into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. PotassiumO-ethyl N- isopropylthiolophosphoramidate (l 1 grams; 0.05 mol) is addedthereto and the reaction mixture is heated at reflux for a period ofabout 18 hours with continuous stirring. After this time the reactionmixture is cooled and filtered to remove the potassium chloride that hasformed. The filtered solution is then stripped of solvent to yield S-(l-methyl-Z-methoxyimino- Z-methoxyethyl) O-ethylN-isopropylthiolophosphoramidate -as a residue.

EXAMPLE l2 Preparation of l-Methoxyiminol-methoxy-2-phenyl-2-chloroethane A newly prepared solution ofdiazomethane (8.4 grams; 0.2 mol) in ether (100 ml.) is placed in al-liter glass reaction flask equipped with a magnetic stirrer, and iscooled to a temperature of about 5 C. A solution ofN-methoxy-a-phenylachloroacetamide (ll grams; 0.l mol) in ether (150ml.) is then added to the reaction flask, with continuous stirring andcooling, over a period of about I hour. After the addition is completed,stirring is continued for a period of about 2 hours. After this time thereaction mixture is stripped of solvent under reduced pressure to yield1 -methoxyimino-l-methoxy- 2-phenyl-2-chloroethane.

EXAMPLE 13 Preparation of O-( l-Phenyl-Z-methoxyimino-2-methoxyethyl)O-Phenyl N-t-Butylphosphoramidate A solution ofl-methoxyimino-l-methoxy-2-phenyl-2- chloroethane (6 grams; 0.05 mol) inmethyl ethyl ketone (100 ml.) is charged into a glass reaction vesselequipped with a mechanical stirrer and reflux condenser PotassiumO-phenyl N-t-butylphosphoramidate l 3.3 grams; 0.05 mol) is added to thereaction vessel and the reaction mixture is heated at reflux withstirring for a period of about 18 hours. After this time the reactionmixture is cooled and filtered to remove the potassium chloride that isformed. The filtered solution is then stripped of solvent under reducedpressure and the residue is redissolved in an ether-methylene chloridemixture. The

resulting solution is then washed with water and is then dried overanhydrous magnesium sulfate. The dried solution is filtered to removethe drying agent and is evaporated to yield 0-(l-phenyl-2-methoxyimino-2-methoxyethyl) O-phenylN-tbutylphosphoramidate as a residue.

EXAMPLE 14 Preparation of l -Methoxyiminol -ethoxy- 2-( 4-chlorophenyl)-2-chloroethane A newly prepared solution of diazoethane (12 grams 0.2mol) is placed into a l-liter glass reaction flask equipped with amagnetic stirrer, and is cooled to a temperature of about 0 C. Asolution of N-methoxy-a-(4-chlorophenyl)-xchloroacetamide (14.5 grams;0.1 mol) in ether (I50 ml.) is then added to the reaction flask, withcontinuous stirring and cooling, over a period of about 2 hours. Afterthe addition is completed, stirring is continued for about 2 hours.After this time the reaction mixture is stripped of solvent underreduced pressure to yieldl-methoxyimino-l-ethoxy-2-(4-chlorophenyl)-2-chloroethane.

EXAMPLE l5 Preparation of S-[ l-(4-chlorophenyl )-2-methoxyimino-2-ethoxyethyl] O-Methyl N-lsopropylthiolophosphoramidate Asolution of l-methoxyimino-l-ethoxy-2-(4-chlorophenyl)-2-chloroethane(l2.8 grams; 0.05 mol) in methyl ethyl ketone (l50 ml.) is charged intoa glass reaction vessel equipped with a mechanical stirrer and refluxcondenser. Potassium O-methyl N-isopropylthiolophosphoramidate (l0grams; 0.05 mol) is added to the flask and the reaction mixture isheated at reflux for a period of about 12 hours. After this time themixture is cooled and filtered to remove the potassium chloride which isformed. The filtered solution is then stripped of solvent under reducedpressure and the residue is redissolved in an ether-methylene chloridemixture. The resulting solution is washed with water and is then driedover anhydrous magnesium sulfate. The dried solution is filtered toremove the drying agent and is evaporated to yield S-l-(4-chlorophenyl)-2-methoxyiminc-Zethoxyethyl10- methylN-isopropylthiolophosphoramidate as a residue.

EXAMPLE 16 Preparation of S-(2-Methoxyimino-2- methoxyethyl)0,0-dimethyl Thionothiolophosphate The reaction mixture was then heatedat reflux, with stirring,v

for a period of about l7 hours. After this time the reaction mixture wasfiltered and the filtrate was distilled to remove the solvent. Theresulting residue was dissolved in ether and the ether solution waswashed with water and aqueous sodium chloride solution and wasthereafter dried over anhydrous magnesium sulfate. The dried solutionwas then stripped of ether under reduced pressure. The residue was thenpurified by chromatography on florex using pentane as the eluent toyield S-(Z-methoxyimino-2-methoxyethyl) 0,0-dimethylthionothiolophosphate having a refractive index at 27 C. of 1.5203.

EXAMPLE 17 Preparation of l-Chloro-Z-ethoxyimino-2-methoxyethane A 40percent aqueous solution of potassium hydroxide (70 m1.) and ether (220ml.) was placed into a 500 ml. Erlenmeyer flask equipped with a magneticstirrer and cooling means. The mixture was then cooled, while stirringin the absence of light, to a temperature of about 3 C.N-Nitrosomethylurea (2.5 grams) was then added to the flask over aperiod of about 5 minutes with continues stirring and cooling. Thereaction mixture was then transferred to a precooled l-liter Erlenmeyerflask and a solution of N-ethoxy-Z-chloroacetamide (18 grams; 0.13 mol)in absolute alcohol (80 ml.) was added thereto over a period of about105 minutes. After the addition was completed, stirring was continuedfor a period of about 1 hour. The reaction mixture was then allowed towarm to room temperature and dried over anhydrous magnesium sulfate. Themixture was filtered and distilled, and the fraction boiling between 62and 65' C. at 13 mm. of Hg pressure was collected to yieldl-chloro-2-ethoxyimino-2-methoxyethane having an index of refraction at25 C. of 1.4556 (D line of sodium) and having the following elementalanalysis as calculated for C .,H,CINO,:

C H N Cl Theoretical 1' 39.6 6.6 9.1 23.

Found i 39.27 6.44 9.14 23.49

EXAMPLE 18 Preparation of S-(2-Ethoxyimino-2- methoxyethyl) 0,0-DimethylThionothiolophosphate -011, H CO-l -S-CH =N-O CgHs1-Chloro-2-ethoxyimino-Z-methoxyethane (3 grams; 0.02 mol), potassium0,0-dimethyl thionothiolophosphate (4 grams; 0.02 mol) and methyl ethylketone 100 ml.) were charged into a reaction vessel equipped with amechanical stirrer and reflux condenser. The reaction mixture was heatedat reflux for a period of about 18 hours. After this time the reactionmixture was cooled and filtered. The filtrate was then stripped ofsolvent and was redissolved in ether. The ether solution was washed withwater and dried over anhydrous magnesium sulfate. The dried solution wasfiltered and evaporated under reduced pressure to yieldS-(2-ethoxyimino- Z-methoxyethyl) 0,0-dimethyl thionothiolophosphate asa residue having a refractive index of 1.51 15 at 25' C.

EXAMPLE 19 Preparation of S-( 2-Methoxyimino 2- ethoxyethyl)0,0-Dimethy1 Thionothiolophosphate l-Chloro2-methoxyimino-2-ethoxyethane(2.3 grams; 0.015 mol), potassium 0,0-dimethyl dithiophosphate (3 grams;0.015 mol) and methyl ethyl ketone ml.) were charged into a glassreaction vessel equipped with a mechanical stirrer and reflux condenser.The reaction mixture was then heated at reflux, with stirring, for aperiod of about 21 hours. After this time the reaction mixture wascooled and filtered to remove the potassium chloride which had formed.The filtrate was evaporated under reduced pressure and the residue wasdissolved in ether containing a small amount of methylene chloride. Theether solution was then washed with water and dried over anhydrousmagnesium sulfate. The dried solution was stripped of solvent underreduced pressure to yield S-(2-methoxyimino-2-ethoxyethyl) 0,0dimethylthionothiolophosphate having a refractive index of 1.5156 at 24 C.

EXAMPLE 20 Preparation of O-(2-Methoxyimino-2 -methoxyethyl)0,0-Diphenyl Phosphate A solution of1-chloro-2-methoxyimino-2-methoxyethane (5.5 grams; 0.04 mol) in methylethyl ketone (100 ml.) is placed into a glass reaction flask equippedwith a mechanical stirrer and reflux condenser. Potassium 0,0-diphenylphosphate (1 1.8 grams; 0.04 mol) is added to the flask and theresulting reaction mixture is heated at reflux for a period of about 20hours. After this time the reaction mixture is cooled and filtered toremove the potassium chloride which is formed. The filtrate is thenstripped of solvent and the residue is dissolved in ether. The ethersolution is washed with water and dried over magnesium sulfate. Thedried solution is evaporated under reduced pressure to yieldO-(Z-methoxyimino-Z-methoxyethyl) 0,0-diphenyl phosphate.

EXAMPLE 21 Preparation of 0-( n-Butoxyimino-Z- ethoxyethyl)O-(4-Chlorophenyl) O-Methyl Phosphate O-CH;

A solution of 1-chloro-2-n-butoxyimino-2-ethoxyethane (9.7 grams; 0.05mol) in methyl ethyl ketone (100 ml.) is placed into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. PotassiumO-(4-chlorophenyl) O-methyl phosphate (12.5 grams; 0.05 mol) is addedand the reaction mixture is heated at reflux, with stirring, for aperiod of about 18 hours. After this time the reaction mixture is cooledand filtered to remove the potassium chloride which has formed. Thefiltered solution is then stripped of solvent and the residue isdissolved in ether. The ether solution is then washed with water, isdried and then evaporated to yield O-(nbutoxyimino-2-ethoxyethyl)O-(4-chlorophenyl) O-methyl phosphate.

Example 22 Preparation of S-( l-Methyl-2-methoxyimino-2-methoxyethyl)0,0-Dimethyl Thiolophosphate A solution ofl-methoxyimino-l-methoxy-2-chloropropane (7.6 grams; 0.05 mol) in methylethyl ketone is charged into a glass reaction flask equipped with amechanical stirrer and reflux condenser. Potassium 0,0-dimethylthiolophosphate (8 grams; 0.05 mol) is added thereto and the reactionmixture is heated at reflux for a period of about 20 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride that is formed. The filteredsolution is then stripped of solvent and the residue is dissolved inether. The ether solution is washed with water and dried over anhydrousmagnesium sulfate. The dried solution is evaporated under reducedpressure to yield S-( l-methyl-2- methoxyimino-Z-methoxyethyl)0,0-dimethyl thiolophosphate.

EXAMPLE 23 Preparation of O-( l-Phenyl-2-methoxyimino-Z-methoxyethyl)O-Methyl O-( 4-Chlorophenyl) Phosphate O-CH;

A solution of l-methoxyiminol -methoxy-2-phenyl-2- chloroethane (8.3grams; 0.05 mol) in methyl ethyl ketone l00 ml.) is charged into a glassreaction vessel equipped with a mechanical stirrer and reflux condenser.Potassium 0- methyl O-(4-chlorophenyl) phosphate (12.5 grams; 0.05 mol)is added to the reaction vessel and the reaction mixture is heated atreflux, with continuous stirring, for a period of about 18 hours. Afterthis time the reaction mixture is cooled and filtered to remove thepotassium chloride that is formed. The filtered solution is stripped ofsolvent and the residue is dissolved in ether. The ether solution iswashed with water and is dried over anhydrous magnesium sulfate. Thedried solution is then evaporated under reduced pressure to yield O-(l-phenyl- 2-methoxyiminoQ-methoxyethyl) O-methyl O-( 4- chlorophenyl)phosphate.

EXAMPLE 24 Preparation of l-Methoxyiminol -methoxy-2-( 2-methylphenyl)-2-chloroethane A newly prepared solution of diazomethane (8.4 grams;0.2 mol) in ether (I00 ml.) is placed in a l-liter glass reaction flaskequipped with a magnetic stirrer and is cooled to a temperature of about5 C. A solution of N-methoxy-a-(Z- methylphenyl)-a-chloroacetamide (12grams; 0.1 mol) in ether (150 ml.) is then added to the reaction flask,with continuous stirring and cooling, over a period of about 1 hour.After the addition is completed. stirring is continued for a period ofabout 1 hour to ensure the completion of the reaction. After this timethe reactioTrnix ture is stripped of solvent under reduced pressure toyield l-methoxyimino-l-methoxy-Z -(2methylphenyl)-2-chloroethane.

EXAMPLE 25 Preparation of S-[ l-( 2-Methylphenyl)-2-methoxyimino-Z-methoxyethyl]O-Methyl O-( 3 ,4-Dicholorophenyl)Thiolophosphate O-CHa A solution of l -methoxyiminol -methoxy-2-( 2-methylphenyl)-2-chloroethane (9 grams; 0.05 mol) in methyl ethyl ketoneml.) is charged into a glass reaction vessel equipped with a mechanicalstirrer and reflux condenser. Potassium O-methyl O-(3,4-dichlorophenyl)thiolophosphate (l5 grams; 0.05 mol) is added to the reaction vessel andthe reaction mixture is heated at reflux, with stirring, for a period ofabout 18 hours. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride that is formed. The filteredsolution is stripped of solvent and the resulting residue is redissolvedin ether. The ether solution is washer with water, dried over magnesiumsulfate, and is evaporated under reduced pressure to yield S-[1-(2-methylphenyl)-2-methoxyimino-2-methoxyethyl]Omethyl O-(3,4'dichlorophenyl) thiolophosphate.

EXAMPLE 26 Preparation of O-( 2-Methoxyimino-2- methoxyethyl) O-MethylMethylphosphonate A solution of l-chloro-2-methoxyimino-2-methoxyethane(7 grams; 0.05 mol) in methyl ethyl ketone I00 ml.) is placed in a glassreaction flask equipped with a mechanical stirrer and reflux condenserPotassium O-methyl methylphosphonate (7.4 grams; 0.05 mol) is added andthe reaction mixture is heated at reflux, with stirring, for a period ofabout 18 hours. After this time the reaction mixtureis cooled andfiltered to remove the potassium chloride which is formed. The filteredsolution is stripped of solvent and the residue is redissolved in ether.The ether solution is washed with water and is dried over anhydrousmagnesium sulfate. The dried solution is then evaporated under reducedpressure to yield O-(Z-methoxyimino-Z-methoxyethyl) O-methylmethylphosphonate.

EXAMPLE 27 Preparation of S-( 2-Methoxyimino-2' methoxyethyl) O-MethylPhenylthionothiolophosphonate l-Chloro-2-methoxyimino-2-methoxyethane(3.5 grams; 0.025 mol), potassium O-methyl phenylthionothiolophosphonate(6 grams; 0.025 mol) and methyl ethyl ketone 100 ml.) were charged intoa glass reaction flask equipped with a mechanical stirrer and refluxcondenser. The reaction mixture was then heated at reflux, withcontinuous stirring, for a period of about 18 hours. After this time themixture was cooled and filtered to remove the potassium chloride thathad formed. The filtrate was evaporated and the resulting residue wasdissolved in ether containing a small amount of methylene chloride. Theether solution was washed with water and was dried over anhydrousmagnesium sulfate. The dried solution was then stripped of solventsunder reduced pressure to yield S-(2-methoxyimino-2-methoxyethyl)O-methyl phenylthionothiolophosphonate as the residue having arefractive index at 25 C. of 1.5789.

EXAMPLE 28 Preparation of S-(2-Ethoxyimino-2- methoxyethyl) O-MethylPhenylthiolothionophosphonate OCH;

l-Chloro-2-ethoxyimino-2-niethoxyethane (3 grams; 0.02 mol), potassiumO-methyl phenyl thiolothionophosphonate grams; 0.02 mol) and methylethyl ketone (100 ml.) were charged into a glass reaction vesselequipped with a mechanical stirrer and reflux condenser. The reactionmixture was heated at reflux, with continuous stirring, for a period ofabout 18 hours. After this time the mixture was cooled and filtered toremove the potassium chloride that had formed. The filtrate wasevaporated and the resulting residue was dissolved in ether. The ethersolution was washed twice with water and was dried over anhydrousmagnesium sulfate. The dried solution was then stripped of ether underreduced pressure to yield S- (2-ethoxyimino-2-methoxyethyl) O-methylphenylthiolothionophosphonate as a residue having a refractive index at17 C. of 1.5720.

EXAMPLE 29 Preparation of S-( 2-Methoxyimino-2- ethoxyethyl) O-MethylPhenylthiolothionophosphonate l OCH;

l-Chloro-2-methoxyimino-2-ethoxyethane (2.3 grams; 0.015 mol), potassiumO-methyl phenylthiolothionophosphonate (3.5 grams; 0.015 mol) and methylethyl ketone (100 ml.) were charged into a glass reaction vesselequipped with a mechanical stirrer and reflux condenser. The reactionmixture was then heated at reflux, with stirring, for a period of about20 hours. After this time the mixture was cooled and filtered to removethe potassium chloride which had fonned. The filtered solution wasevaporated and the resulting residue was dissolved in ether containingsmall amounts of methylene chloride. This solution was washed withwater, was dried over anhydrous magnesium sulfate and was filtered. Thefiltrate was then stripped of solvents under reduced pressure to yieldS-(2-methoxyimino-2- ethoxyethyl) O-methyl phenylthiolothionophosphonatehaving a refractive index of 1.5540 at 25 C.

EXAMPLE 30 Preparation of l-Chloro-2-ethoxyimino-2-ethoxyethane EXAMPLE31 Preparation of S-( 2-Ethoxyimino 2- ethoxyethyl) OMethylPhenylthiolothionophosphonate l-Chloro-2-ethoxyimino-2-ethoxyetha.ne(2.5 grams; 0.015 mol), potassium O-methyl phenylthiolothionophosphonate(3.5 grams; 0.015 mol) and methyl ethyl ketone ml.) were charged into aglass reaction flask equipped with a mechanical stirrer and refluxcondenser. The reaction mixture was heated at reflux for a period ofabout 8 hours. After this time the mixture was filtered to remove thepotassium chloride that had formed. The filtrate ww stripped of solventand the resulting residue was dissolved in ether containing a smallamount of methylene chloride. This solution was washed with water, driedover magnesium sulfate and filtered. The filtrate was evaporated underreduced pressure to yield S-(2- ethoxyimino-2-ethoxyethyl) O-methylphenylthiolothionophosphonate as a residue having a refractive index at25 C. of 1.5431.

EXAMPLE 32 Preparation of S'( 2-Methoxyimino-2- ethoxyethyl) O-Ethyllsopropylthiolophosphonate 1-Chloro-2-methoxyirnino-2-ethoxyethane (4.5grams; 0.03 mol), potassium O-ethyl isopropylthiolophosphonate (6 grams;0.03 mol) and methyl ethyl ketone ([00 ml.) are charged into a glassreaction flask equipped with stirrer and reflux condenser. The reactionmixture is heated at reflux for a period of about 16 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride which has formed. The filteredsolution is then evaporated under reduced pressure and the residuedissolved in an ether-methylene chloride mixture. The resulting solutionis washed with water and is dried over anhydrous magnesium sulfate andfiltered. The filtered solution is then stripped of solvents underreduced pressure to yield S-(2- methoxyimino-2-ethocyethyl) Oethylisopropylthiolophosphonate.

EXAMPLE 33 Preparation of O-( 2-Methoxyimino-2- ethoxyethyl) O-Ethyl4-Chlorophenylphosphonate l-Chloro-2-methoxyimino-2-ethoxyethane (4.5grams; 0.03 mol), potassium 0ethyl 4-chlorophenylphosphonate (7.7 grams;0.03 mol) and methyl ethyl ketone (100 ml.) are charged into a glassreaction flask equipped with stirrer and reflux condenser. The reactionmixture is heated at reflux for a period of about 16 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride which has formed. Thejiltereds 9lgt io n is then evaporated under reduced pressure and the residuedissolved in an ether-methylene chloride mixture. The resulting solutionis washed with water and is dried over anhydrous magnesium sulfate andfiltered. The filtered solution is then stripped of solvents underreduced pressure to yield O-(2- methoxyimino-Z-ethoxyethyl) O-ethyl4-chlorophenylphosphonate.

EXAMPLE 34 Preparation of O-(2-Methoxyimino-2- methoxyethyl) O-PhenylPhenylph'osphonate O-CH:

A solution of l-chloro-Z-methoxyimino-2-methoxyethane (7 grams; 0.05mol) in methyl ethyl ketone I00 ml.) is placed into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. PotassiumO-phenyl phenylphosphonate l3 grams; 0.05 mol) is added and the reactionmixture is heated at reflux, with stirring, for a period of about l8hours. After this time the reaction mixture is cooled and filtered toremove the potassium chloride which is fonned. The filtered solution isthen stripped of solvent under reduced pressure and the residue isredissolved in an ether-methylene chloride mixture. The resultingsolution is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is then filtered and evaporated to. yieldO-( Z-methoxyimino-Z-methoxyethyl) O-phenyl phenylphosphonate.

EXAMPLE 35 Preparation of S-( l-Methyl-Z-methoxyimino-Z-methoxyethyl)O-Methyl Methylthiolophosphonate A solution ofl-methoxyimino-l-methoxy-2-chloropropane (7.6 grams; 0.05 mol) in methylethyl ketone is charged into a glass reaction flask equipped with amechanical stirrer and reflux condenser. Potassium O-methylmethylthiolophosphonate (7.2 grams; 0.05 mol) is added thereto and thereaction mixture is heated at reflux for a period of about 20 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride that is formed. The filteredsolution is then stripped of solvent and the residue is dissolved inether. The ether solution is washed with water and dried over anhydrousmagnesium sulfate. The dried solution is evaporated under reducedpressure to yield S-( l-methyl-2-methoxyimino-2- methoxyethyl) O-methylmethylthiolophosphonate.

, EXAMPLE 36 Preparation of O( l-Phenyl-2-methoxyimino-2-methoxyethyl)OMethyl (4-Chlorophenyl)phosphonate A solution ofl-methoxyimino-l-methoxy-2-phenyl-2- chloroethane (8.3 grams; 0.05 mol)in methyl ethyl ketone ml.) is charged into a glass reaction vesselequipped with a mechanical stirrer and reflux condenser. Potassium 0-methyl (4-chlorophenyl)phosphonate (1 L7 grams; 0.05 mol) is added tothe reaction vessel and the reaction mixture is heated at reflux, withcontinuous stirring, for a period of about 18 hours. After this time thereaction mixture is cooled and filtered to remove the potassium chloridethat is formed. The filtered solution is stripped of solvent and theresidue is dissolved in ether. The ether solution is washed with waterand is dried over anhydrous magnesium sulfate. The dried solution is theevaporated under reduced pressure to yield O-( l-phenyl-2-methoxyimino-2-methoxyethyl) O-methyl (4-chlorophenyl)phosphonate.

EXAMPLE 37 Preparation of S-[-(2-Methylphenyl)-2-methoxyimino-Z-methoxyethyl 10-( 3,4- Dichlorophenyl)Methylthiolophosphonat @4H; Cl

a mechanical refluifohderiseiil otassium O-( 3.4- V

dichlorophenyl methylthiolophosphonate (14.2 grams; 0.05 mol) is addedto the reaction vessel and the reaction mixture is heated at reflux,with stirring, for a period of about 18 hours.

After this time the reaction mixture is cooled and filtered to removethe potassium chloride that is formed. The filtered solution is strippedof solvent and the resulting residue is redissolved in ether. The ethersolution is washed with water, dried over magnesium sulfate, andis'evaporated under reduced pressure to yieldS-[1-(2-methylphenyl)-2-methoxyimino-2- methoxyethyi O-( 3,4-dichlorophenyl) methylthiolophosphonate.

EXAMPLE 38 Preparation of O-( 2-Methoxyimino-2- methoxyethyl)Dimethylphosphinate A solution of l-chloro-2-methoxyimino-2-methoxyethane (7 grams; 0.05 mol) in methyl ethyl ketone (100 ml.) is placedinto a glass reaction flask equipped with a mechanical stirrer andreflux condenser. Potassium dimethylphosphinate (6.6 grams; 0.05 mol) isadded and the reaction mixture is heated at reflux with stirring, for aperiod of about 18 hours. After this time the reaction mixture is cooledand filtered to remove. the potassium chloride which is formed. Thefiltered solution is then stripped of solvent under reduced pressure andthe residue is redissolved in an ether-methylene chloride mixture. Theresulting solution is washed with water and dried over anhydrousrnagnesium sulfate. The dried solution is then filtered and evaporatedto yield O-(2-methoxyimino-Z-methoxyethyl) dimethylphosphinate.

EXAMPLE 39 Preparation of S-(2-Methoxyimino-2- ethoxyethyl)Diisopropylthiolophosphinate l-Chloro-2-methoxyimino-2-ethoxyethane (4.5grams; 0.03 mol), potassium diisopropylthiolophosphinate (6.1 grams;0.03 mol) and methyl ethyl ketone (100 ml.) are charged into a glassreaction flask equipped with stirrer and reflux condenser. The reactionmixture is heated at reflux for a period of about 16 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride which is formed. The filteredsolution is then evaporated under reduced pressure and the residuedissolved in an ether-methylene chloride mixture. The resulting solutionis washed with water and is dried over anhydrous magnesium sulfate andfiltered. The filtered solution is then stripped of solvents underreduced pressure to yield S-(2-methoxyimino- 2-ethoxyethyl)diisopropylthiolophosphinate.

EXAMPLE'W Preparation of O-( 2-n-Butoxyimino- 2-ethoxyethyl) (4-Chlorophenyl)methylphosphinate CH s A solution ofl-chloro-2-n-butoxyimino-2-ethoxyethane (9.7 grams; 0.05 mol) in methylethyl ketone (100 ml.) is placed into a glass reaction flask equippedwith a mechanical stirrer and reflux condenser. Potassium (4-chlorophenyl)methylphosphinate (l 1.4 grams; 0.05 mol) I added and thereaction mixture is heated at reflux, with stirring, for a period ofabout 18 hours. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride which has formed. The filteredsolution is then stripped of solvent under reduced pressure and theresidue is redissolved in an ether-methylene chloride mixture. Theresulting solution is washed with water and is dried over anhydrousmagnesium sulfate. The dried solution is then filtered and evaporated toyield O-(2-n-butoxyimino-2-ethoxyethyl)(4-chlorophenyl)methylphosphinate.

EXAMPLE 41 Preparation of S-( 2-lsopropoxyimino- 2-methoxyethyl)Benzylphenylthiolothionophosphinate O-CH; C

A solution of l-chloro-Z-isopropoxyimino-2-methoxyethane (8.5 grams;0.05 mol) in methyl ethyl ketone ml.) is placed into a glass reactionflask equipped with a mechanical stirrer and reflux condenser. Potassiumbenzylphenylthiolothionophosphinate (15 grams; 0.05 mol) is added to theflask and the reaction mixture is heated at reflux for a period of about12 hours. After this time the reaction mixture is cooled and filtered toremove the potassium chloride which has formed. The filtered solution isthen stripped of solvent under reduced pressure and the residue isredissolved in an ether-methylene chloride mixture. The resultingsolution is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is filtered and stripped of solvent underreduced pressure to yield S-(2- isopropoxyimino-Z-methoxyethyl)benzylphenylthiolothionophosphinate as a residue.

EXAMPLE 42 Preparation of S-( l-Methyl-Z-methoxyimino-2-methoxyethyl)Dimethylthiolophosphinate A solution 6? l -n'iethoxyiminolniethoxy-2-chloroprop ane (7.6 grams; 0.05 mol) in methyl ethyl ketoneis charged into a EXAMPLE 43 Preparation of O-(lPhenyl-Z-methoxyimino-2-methoxyethyl) (4-Chlorophenyl)methylphosphinateA solution of 1-methoxyimino-l-methoxy-2-phenyl-2- chloroethane (8.3grams; 0.05 mol) in methyl ethyl ketone (100 ml.) is charged into aglass reaction vessel equipped with a mechanical stirrer and refluxcondenser. Potassium (4- chlorophenyl)methylphosphinate (10.7 grams;0.05 mol) is added to the reaction vessel and the reaction mixture isheated at reflux, with continuous stirring, for a period of about 18hours. After this time the reaction mixture is cooled and filtered toremove the potassium chloride that is formed. The filtered solution isstripped of solvent and the residue is dissolved in ether. The ethersolution is washed with water and is dried over anhydrous magnesiumsulfate. The dried solution is then evaporated under reduced pressure toyield O-( l-phenyl- 2-methoxyimino-Z-methoxyethyl)(4-chlorophenyl)methylphosphinate.

EXAMPLE Preparation of S-[ l-(2-Methylphenyl)-2-methoxyimino-2-methoxyethyl] (3,4-

Dichlorophenyl)methylthiolophosphinate OCH;

A solution of l'methoxyimino-l-methoxy-2-(2-methylphenyl)-2-chloroethane (9 grams; 0.05 mol) in methyl ethyl ketone (100ml.) is chargedinto a glass reaction vessel equipped with a mechanicalstirrer and reflux condenser. Potassium 3 ,4-dichlorophenyl)methylthiolophosphinate (13.2 grams; 0.05 mol) is added to the reactionvessel and the reaction mixture is heated at reflux, with stirring, fora period of about 18 hours. After this time the reaction mixture iscooled and filtered to remove the potassium chloride that is formed. Thefiltered solution is stripped of solvent and the resulting residue isredissolved in ether. The ether solution is washed with water, driedover magnesium sulfate. and is evaporated under reduced pressure toyield S-[l-(2- 20 methylphenyl)-2-methoxyimino-2-methoxyethyl]dichlorophenyl methylthiolophosphinate.

Other nematocidally active compounds within the scope of this inventionwhich can be prepared by the procedures described in the foregoingexamples are:

O-(2-methoxyimino-2-methoxyethyl) O-(4-bromophenyl)N,N-di-n-butylphosphoramidate O-(2-methoxyimino-Z-ethoxyethyl)O-(4-methoxyphenyl) N,N-diethylphosphoramidate0-(2-n-butoxyimino-2-ethoxyethyl) S-(2,4-dinitrophenyl)N-isopropylthiolophosphoramidate S-( 2-isopropoxyimino-2-methoxyethyl)O-( 3- methylthiophenyl) N,N-dimethylthiolophosphoramidateO-(2-methoxyimino-Z-methoxyethyl) O-(4-rnethylsulfinylphenyl)N-methylphosphoroamidate 0-(2methoxyimino-2-ethoxyethyl) O-(3-ethylsulfonylphenyl) N,N-di-n-decylphosphoramidate O-(2-ethoxyimino-Z-methoxyethane) S-n-propyl N,N-

dimethylthiolophosphoramidate S-( 2-methoxyimino-2-methoxyethyl) S-(4-dimethylaminophenyl) N-ethyldithiolophosphoramidate O-(2-n-propoxyimino-Z-methoxyethyl) O-ethyl N-isopropylthionophosphorarnidate O-( 2-methoxyimino-Z-methoxyethyl)S-ethyl N,N-

dimethylthiolothionophosphoramidate S-( 2-n-butoxyimino-Z-methoxyethyl)chlorophenyl) dimethylthiolothionophosphoramidate O(2-methoxyimino-2-octyloxyethyl) ethylphosphonamidateO-(2-methoxyimino-2-ethoxyethyl) 3,4-dichlorobenzyl-N-ethylthionophosphonamidate 4-chlorophenyl-N- S-(2-methoxyimino-2-methoxyethyl) phenyl-N,N-

dimethylthiolophosphonamidate S-( 2-ethoxyimino-Z-n-propoxyethyl)2-methoxy-4- chlorobenzyl-N-isopropylthiolothionophosphonamidate 0-(l-ethyl-2-methoxyimino-Z-methoxyethyl) O-(4- methylphenyl)N-n-propylphosphoramidate 0-( l-phenyl-2-methoxyimino-Zn-butoxyethyl) IO-ethyl N,N-dimethylphosphoramidate O-[ l-(3-dimethylaminophenyl)-2-ethoxyimino-2-methoxyethyl]O-(2-methyl-4-chlorophenyl) N,N- diethylphosphoramidate O-[l-(2,4-dichlorophenyl )-2-methoxyimino-Z-ethoxyethyl] O-(3-ethylsulfonylphenyl) N-ethylphosphoramidate O-[l-(4-bromophenyl)-2-methoxyimino-Z-methoxyethyl] S-ethylN-methylthiolophosphoramidate S-[ l-(2-methyl-4-chlorophenyl)-2-methoxyimino-2- methoxyethyl] S-benzylN-methyldithiolophosphoramidate O-[l-3-nitrophenyl)-2-methoxyimino-Z-methoxyethyl] ethylN-isopropylthiolothionophosphoramidate 0-(1-ethyl-2-ethocyimino-2-methoxyethyl)4-chlorophenyl-N-methylphosphonamidate O-(l-phenyl-2-methoxyimino-2-methoxyethyl) butylthionophosphonamidate 0-[l-( 2,4-dibromophenyl )-2-rnethoxyimino-Z-methoxyethyl]3-bromophenyl-N-isopropylphosphonamidate S-(l-methyl-2-methoxyimino-Z-methoxyethyl) phenyl-N-isopropylthiolophosphonamidate O-(l-n-butyl-Z-methoxyimino-Z-methoxyethyl) 2-methyl-4-chlorophenyl-N-isopropylphosphonamidate ethyl-N-t- O[ l-( 4-allylphenyl)-2-methoxyimino-2-methoxyethyl] nitrophenyl N,N-dimethylphosphonamiditeO-(Z-methbxyimino-Z-methoxyethyl) 0,0dimethyl phosphate0-(2-methoxyimino-2-ethoxyethyl) O-methyl O-isopropyl phosphate 7 0-(2-ethoxyimino-Z-methoxyethane) 0,0-di-n-butyl thionophosphate O-(Z-methoxyimino-Z-methoxyethyl) methylphenyl) O-methyl phosphateO-(2-methoxyimino-Z-methoxyethyl) O-(3-nitrophenyl) O- 25 methoxyethyl]N-t-butyl-4-n-pentylsulfofiylph?nyi dithiophosphonamidate O-(Z-methoxyimino-2-methoxyethyl) phenethyldithiolophosphate S-isopropyl S-O-(2-methoxyimino-2 ethoxyethyl) O-(4-chlorphenyl) O-(2-ethoxy-4,5-dibromophenyl) phosphate O-( 2-ethoxyimino-2-methoxyethyl)phosphate O-( Z-ethoxyimino-Z-ethoxyethyl) O-(3-iodophenyl) o-( 3-isopropoxy-S-n-pentylphenyl) phosphate O-(2-methoxyimino-2-methoxyethyl)O-(2,6-diethoxyphenyl O-(4-n-propylsulfonylphenyl) phosphateO-(Z-methoxyimino-2-methoxyethyl) O-( 3-n-butylthiophenyl)O-(4-ethylsulfinylphenyl) phosphate 0,0-di-n-decyl O-(2-methoxyimino-2-methoxyethyl) S-( 2,4-dinitrophenyl) S-( 3,4-dichlorophenyl) dithiolophosphate O-(2-methoxyimino-2n-octyloxyethyl) 0-(2di-npropylamino-4,5-dichlorophenyl) O-(4-hexyloxyphenyl) phosphate O-(2-n-pentyloxyimino-2-methoxyethyl) O-( 3-hexyloxy-5- fluorophenyl)O-(4-n-decylphenyl) phosphate O-(l-methyl-2-methoxyimino-2-methoxyethyl) 0,0-

dimethyl phosphate 0-( l-allyl-2-methoxyimino-2-methoxyethyl)O-isopropyl O-phenyl phosphate 0-(1-ailyloxy-Z-methoxyimino-2-methoxyethyl) O-methyl O-(3-methylphenyl)phosphate O-( l-pentenyloxy-Z-ethoxyimino-Z-methoxyethyl) benzylO-phenyl phosphate O-(l-pentenylthio-2-t-butylimino-2-methoxyethyl)O-(4-tbutylphenyl) O-(4-chlorophenyl) phosphate 0-[ l-(3-chloro-4-nitrophenyl)-2-methoxyimino-2-methoxyethyl]0-(4-pentylsulfinylphenyl) S-(2-methoxybenzyl) thiolophosphate O-[l-(4-butylthiophenyl)-2methoxyimino-2-methoxyethyl]O-(Z-pentyloxyphenyl) O-(3,4-diiodobenzyl) phosphate 0-[l-(2,6-dimethoxyphenyl)-2-methoxyimino-2methoxy y nitrobenzyl)thiolothionophosphate 0-( l-phenyl-2-methoxyimino-2-n-butoxyethyl)S-(4-dihexylaminophenyl) S -(3,4-dichlorophenyl) dithiolophosphate O-(l-octyl-2-ethoxyimino-2-methoxyethyl) S-( 3-decyloxyphenyl)S-(4-n-butylsulfinylphenyl) dithiolophosphate S-(l-hexyloxy-Z-methoxyimino-2-methoxyethyl) 0-[3-(4-methylphenyl)-propyl]O (4-bromobenzyl) thiolothionophosphate S-[ l-(3-phenylpropyl )-2-methoxyimino-2-methoxyethyl] S,S-dimethyltetrathiophosphate S-[ i-( 3-hexenylphenyl)-2-methoxyimino-2-methoxyethyl] S-(4-isopropylsulfonylphenyl)S-(B-methylthiophenyl) trithiolophosphate O-(l-methyl-2-methoxyimino-Z-methoxyethyl) O-methyl methylphosphonateO-(l-ailyl-2-methoxyimino-Z-methoxyethyl) O-isopropyl phenylphosphonateO-( l-allyloxy-2-methoxyimino-Z-methoxyethyl) O-methyl 3-methylphenyl)phosphonate O-( l-pentenyloxy-2-ethoxyimino-2-methoxyethyl) O- benzylphenylphosphonate O-( l-pentenylthio-2-t-butylimino-2-methoxyethyl) O-(3- bromophenyl) benzylphosphonate O-(l-decylthio-2-methoxyimino-Z-ethoxyethyl) O-( 4-t-butylphenyl)(4-chlorophenyl)phosphonate O-[ l-(3-chloro-4-nitrophenyl)-2-methoxyimino-2-methoxyethyl]0-(4-pentylsulfinylphenyl) (2-methoxybenZyDphosphonate O-[l-(4-butylthiophenyl)-2-methoxyimino-2-methoxyethylO-(2-pentyloxyphenyl) (3,4-diiodobenzyl) phosphonate 0-[ l-(2,o-dimethoxyphenyl)-2-methoxyimino-2-methoxyethyl]0-[3-(3,4-dichlorophenyD-propyl] (3- nitrobenzyl)thionophosphonate O-(l-phenyl-2-methoxyimino-2-n-butoxyethyl) S-(4-dihex- Eminophenyl) (3,4-dichlorophenyl)thiolophosphonate O-[3-(3,4-dichlorophenyl)-propyl]S-( 3- O-(l-octyl-2-ethoxyimino-2-methoxyethyl) S-(3-decyloxyphenyl)(4-n-butylsulfinylphenyl)thiolophosphonateS-(l-hexyloxy-2-methoxyimino-2-methoxyethyl) 0-[3-(4-methylphenyl)-propyl] (4- bromobenzyl)thiolothionophosphonate S-[l-(3-phenylpropyl)-2-methoxyimino-Z-methoxyethyl] S- methylmethyltrithiophosphonate S-[ l(3-hexenylphenyl)-2-methoxyimino-2-methoxyethyl] S-( 4-isopropylsulfonylphenyl)(S-methylthiphenyl trithiophosphonate 0-(l-methyl-2-methoxyimino-2-methoxyethyDdimethylphosphinate 0-(l-allyl-2-methoxyimino-Z-methoxyethyi) isopropylphenylphosphinate O-(l-allyloxy-2-methoxyimino-2-methoxyethyl) methylphenyl)methylphosphinateO-( l-pentenyloxy-Z-ethoxyimino-Z-metboxyethyl) benzylphenylphosphinate0-( l-pentenylthio-2-t-butylimino-2-methoxyethyl)bromophenyl)benzylphosphinate 0-(l-decylthio-2-methoxyimino-2-ethoxyethyl) tylphenyl)(4-chlorophenyl)phosphinate S-[ 1-(3-chloro-4-nitrophenyl)-2mino-Z-methoxyethyl] [3-(3,4-dichlorophenyl)-pr0pyl] 3 -nitrobenzyl)thionophosphinate O-( l-phenyl-2-methoxyimino-2-n-butoxyethyl)(4-dihexylaminophenyl) (3,4-dichlorophenyl)phosphinate S-(l-octyl-2-ethoxyimino-2-methoxyethyl) (3-decyloxyphenyl)(4n-butysulfinylphenyl)thiolophosphinate S-( l-hexyloxy-2-methoxyimino-2-methoxyethyl) [3-(4- methylphenyl)-propyl](4- bromobenzyl)thiolothionophosphinate S-[ l-(3-phenylpropyl)-Z-methoxyimino-2-methoxyethyl] dimethylthiolophosphinateS-[ l-( 3-hexenylphenyl )-2-methoxyimino-Z-rnethoxyethyl](4-isopropylsulfonylphenyl) (3-methylthiophenyl thiolophosphinata, andthe like.

For practical use as nematocides, the active compounds of this inventionare generally incorporated into nematocidal compositions which comprisean inert carrier and a nematocidally toxic amount of such a compound.Such compositions, which can also be called formulations, enable theactive compound to be applied conveniently to the site of the nematodeinfestation in any desired quantity. These compositions can be solidssuch as dusts, granules or wettable powders; or they can be liquids suchas solutions, aerosols or emulsifiable concentrates.

Y dust compositions.

in some cases the active compounds ares ufiiciently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofnematocides can be dispersed under superatmospheric pressure asaerosols. However, preferred liquid nematocidal compositions areemulsifiable concentrates, which comprise an active compound accordingto this invention and as the inert carrier, a solvent and an emulsifier.Such emulsifiable concentrates can be extended with water tion. Theemulsifiers most commonly used in these concentrates are nonionic ormixtures of nonionic with anionic surface-active agents. With the use ofsome emulsifier systems an inverted emulsion (water-in-oil) can beprepared for direct application to nematode infestations.

A typical nematocidal composition according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

EXAMPLE 45 Preparation of a Dust Product of example 2 l Powdered Tale 90The above ingredients are mixed in a mechanical grinderblender and areground until a homogeneous, free-flowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the nematode infestation.

The compounds of this invention can be applied as nematocides in anymanner recognized by the art. One method for the 0 control of nematodescomprises contacting the locus of said nematodes with a nematocidalcomposition comprising an inert carrier and as an essential activeingredient, in a quantity toxic to said nematodes, a compound of thepresent invention.

The concentration of the new compounds of this invention in thenematocidal compositions will vary greatly with the type of formulationand the purpose for which it is designed, but generally the compositionswill comprise from about 0.05 to about 95 percent by weight of theactive compounds of this invention. In a preferred embodiment of thisinvention, the neparasitic nematodes occur in enormous numbers in allkinds of soil in which plants can grow, and many plant pathologistsbelieve that all the crop and ornamental plants grown in the world canbe attacked by these nematodes. The destructive species of nematodesrange from the highly specialized, which attack only a few kinds ofplants, to the polyphagous, which attack a great many different plants.The plants almost invariably become infected by nematodes that move intothem from the soil. The underground parts of plants, roots, tubers,

corns and rhizomes are thus more apt to be infected than abovegroundparts, but infection of stems, leaves and flower parts is also fairlycommon.

Damage to plants attacked by nematodes is due primarily to the feedingof the nematodes on the plant tissues. The nematodes may enter the plantto feed, may feed from the outside, or be only partially embedded. Thefeeding of a nematode may kill the cell or may simply interfere with itsnormal functioning. If the cell is killed, it is often quickly invadedby bacteria or fungi. if the cell is not killed, it and the adjacentcells may be stimulated to enlarge or multiply. Hence the most commontypes of nematode damage are manifest as rotting of the attacked partsand adjacent tissue or the development of galls and other abnormalgrowths. Either can interfere with the orderly development of the plantand cause shortening of stems or roots, twisting, crinkling or death ofparts of stems and leaves, and other abnormalities. Consequently, theyield of crop plants is reduced, while a high-quality crop cannot beproduced from the crippled plants.

The use of the compounds of this invention for nematode control can makethe difference between a good crop and one not worth harvesting. Oncethe nematodes are controlled, yield increases of 25 to 50 percent arenot uncommon. The solid or liquid nematocidal compositions of thisinvention can be applied to the soil, or in some cases to the plants andsoil, in

any gorrvenient manner. While broadcast applications tqthe aoil beforeplanting by conventional plow or disc method are effective, specializedmethods such as row placement application, split-dosage applications,postplanting sidedress applications, and the like are also useful.

The nematocidal activity of the compounds of this invention can be shownby a variety of testing techniques known to the art. For example, in oneseries of tests, compounds of this invention were tested for control ofthe root knot nematode (Meloidogyne spp.) on tomato plants. Thenematodes were reared by blending a part of a 2- to 3-month old cultureof the nematodes with sieved soil (86-inch sieve) and sand in a mixer.The infested soil mixture was placed in 4-inch plastic pots and manuallycompacted. The compounds of the present invention were dissolved in asolvent, such as acetone containing emulsifiers, diluted with water toml. and drenched on the surface of the soil in each pot. The pots wereplaced in a greenhouse and held for 7 days, after which time, 10- to 14-day-old Bonny Best tomato seedlings were transplanted to the soilmixture in each pot. After at least 2 weeks, control of galls on theroots of the plants in the treated soil mixture with the number of gallson plants growing in infested, but untreated soil mixture. The resultsare as follows:

The nematocidal activity of the compounds of the present invention wasalso demonstrated in another test for the control of root knot nematodeon tomato plants. Nematode infested soil and sand mixture (630 ml.),prepared as described above, was placed into a plastic bag. The testsolution of the compounds of the present invention in acetonecontainingemulsifiers was prepared as above and pipetted into each bag.The solution and soil mixture in each bag was mixed and the bag placedin a incubator in the dark at 75 F. for 7 to 10 days. Thereafter thetreated soil mixture was transferred to 4-inch plastic pots which wereplaced in a greenhouse for 7 days. The soil mixture in the pots waswatered daily. After the 7-day period, 10- to l4-day-old Bonny Besttomato seedlings were transplanted to the soil mixture in each pot. Thecontrol of the root knot nematode was determined after at least 2 weeksby comparing the number of galls on the roots of the plants growing ininfested and incubated, but otherwise untreated, soil mixture. The r e su lts we e as follows:

TABLElI Concentration of Test Compound in We claim:

' 1. A nematocidal composition comprising an inert. carrier and, as anessential active ingredient, in a quantity toxic to nematodes, acompound of the formula wherein R and R are lower alkyl; X, X, X and Xare independently selected from the group consisting of oxygen andsulfur; m and n are each integers from to 1; Z is selected wherein A isselected from the group consisting of lower alkyl,

A wherein B is selected from the group consisting of lower alkyl, loweralkenyl, lower alkoxy, lower alkylthio, chlorine, bromine, nitro, loweralkylsulfoxide, lower alkyl sulfone and diamino, r is an integer from 0to 5, Q is selected from the group consisting of oxygen, sulfur, loweralkylene, lower alkyleneoxy and lower alkylenethio, and r is an integerfrom 0 to w The nematocidalcomposition l wheremthe 5E- tive ingredientis S-(2-methoxyimino-2-methoxyethyl) O-ethylN-isopropylthiolophosphoramidate.

3. The nematocidal composition of claim 1 wherein the active ingredientis S-(Z-methoxyimino-2-ethoxyethyl) O-ethylN-isopropylthiolophosphoramidate. h

4. The nematocidal composition of claim 1 wherein the active ingredientis S-(2-ethoxyimino-2-methoxyethyl) O-ethylN:isopropylthiolophosphoramidate.

5. A method for the control of nematodes which comprises contacting saidnematodes, or the locus of said nematodes,

with a nematocidally effective amount of the composition of claim 1.

6. A method for the control of nematodes which comprises contacting saidnematodes, or the locus of said nematodes,

lower alkenyl, lower alkoxy, lower alkylthio, chlorine, with anematocidally effective amount of the composition of bromine, nitro,lower alkylsulfoxide, lower alkylsulfone and diamino, q is an integerfrom 0 to 5, and p is an integer from 0 to 3; Z is selected from thegroup consisting of hydrogen and Z, provided that when 2 is hydrogenthen n is 0; and Y is selected from the group consisting of lower alkyl,lower alkenyl, lower alkoxy, lower alkylthio, amino, lower alkylamino,diamino and claim 2. g v w 7. A method for the control of nematodeswhich comprises contacting said nematodes, or the locus of saidnematodes,

' with a nematocidally effective amount of the composition of claim 3.

232 3 UNITED STATES, PATENT OFFICE CERTIFICATE OF CORRECTION Patent x0.3' 6 66 Dated November 23, 1971 Sifinoy B. Ric ter and PDhIGiIJJ- KaplanIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In Column 3, line 22 delete "allylphenyfl" In column 4, line 7 4 the "H"appearing over the third column of numerical figures should appear overthe second column.

In column 10, lines 58to 62 the part of the formula appearing as 0 H C1OI|-OCH should read l' C1 0 P- O CH;

OCH

In column 13, lines 27 to 30 the part of the formula appearing as"=-I.'OCEI should read ==N-0C H In column 19, line 2 for "6.7" read--6.6--

mg? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated November25, 1971 Patent No. 5,622,667

I.nventor(s) Sidney B. Richter and Ephraim H. Kaplan page 2 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In column 1 lines 22 to 25 the part of? the formula oooearing as O O H vH -CO should read -'P-- 0- In column 29, line 27 for djmrnino" read --dl(lower '1ll yl):1mi'lno--; and in line '52 ['or "diamino" read--di'flower :'1l1{yl)amino In column ,50, line 1 delete "Ta and in lineLor "diamino" rend -di (lower :llkyl)zimino- Signed and sealed this hthday of July 1972.

(SEAL) Attest:

EDWARD M.FLETCHER JR ROBERT GUTTSCHALK Attesting Officer Commissioner ofPatents

2. The nematocidal composition of claim 1 wherein the active ingredientis S-(2-methoxyimino-2-methoxyethyl) 0-ethylN-isopropylthiolophosphoramidate.
 3. The nematocidal composition ofclaim 1 wherein the active ingredient isS-(2-methoxyimino-2-ethoxyethyl) 0-ethylN-isopropylthiolophosphoramidate.
 4. The nematocidal composition ofclaim 1 wherein the active ingredient isS-(2-ethoxyimino-2-methoxyethyl) 0-ethylN-isopropylthiolophosphoramidate.
 5. A method for the control ofnematodes which comprises contacting said nematodes, or the locus ofsaid nematodes, with a nematocidally effective amount of the compositionof claim
 1. 6. A method for the control of nematodes which comprisescontacting said nematodes, or the locus of said nematodes, with anematocidally effective amount of the composition of claim
 2. 7. Amethod for the control of nematodes which comprises contacting saidnematodes, or the locus of said nematodes, with a nematocidallyeffective amount of the composition of claim
 3. 8. A method for thecontrol of nematodes which comprises contacting said nematodes, or thelocus of said nematodes, with a nematocidally effective amount of thecomposition of claim 4.